FR2467875A1 - ADHESIVE COMPOSITIONS BASED ON RUBBER CURABLE IN ANAEROBIC CONDITIONS AND ARTICLES COMPRISING SAME - Google Patents

Abstract

The invention relates to adhesive compositions. It relates to a cold vulcanizable composition, characterized in that it comprises: a. 30% to 80% by weight of a copolymer selected from an acrylonitrile / butadiene copolymer having terminal or pendant vinyl groups, an acrylonitrile / butadiene copolymer having carboxy, mercapto or amino end groups, polybutadiene, polyisoprene, an acrylonitrile copolymer / butadiene / styrene and a butadiene / styrene copolymer; b. 80% to 20% by weight of an anaerobic monomer which is soluble in or miscible with the copolymer; vs. 0.1% to 7% by weight, based on the weight of the anaerobic monomer, of a catalytic system; d. an accelerator; summer. a stabilizer. Use as sealant, gasket material, etc.

Description

Curable adhesive compositions are known under conditions

  anaerobic and their uses have become increasingly important in the industry as sealants, seals and for their adhesive properties. Anaerobic sealants and adhesives are conventionally used in a form ranging from a liquid consistency such as water to a light fat consistency. The composition

  in this form "wets" the surface to be bonded.

  The conventional anaerobic compositions currently on the market have disadvantages

  for some of their uses.

  The areas of use of the anaerobic compositions could be broadly extended if these

  compositions were in a form with characteristics

  solid characteristics. In addition, many fields of application, such as seams, require that the polymerized (hardened) composition is resistant.

  solvents and retains flexibility.

  Synthetic rubbers have many of these desired properties, but their use is limited because of the relatively harsh conditions required to vulcanize the rubber, such as

  high temperatures or irradiation.

  The present invention combines the technology

  rubber and anaerobic technology to provide a curable composition under anaerobic conditions. An anaerobic system is usually defined as a system that remains stable in its mixed form in the presence of oxygen, but that polymerizes

  to a more highly polymerized state in the absence of oxy-

  gene. This, in fact, means that the presence of oxy-

  gene prevents or delays polymerisation (hardening).

  is lying). Preferably, the anaerobic curing occurs at ambient temperatures; however, the rate of polymerization depends on the monomer, the initiator, and whether inhibitors and / or accelerators are present or not. Thus, the term "anaerobic curing" has been and is used to refer to a polymerization that also occurs at

  temperatures higher than the ambient temperatures

  the main factor being that the hardening

  is inhibited by the presence of oxygen, but is

  in its absence or in a reduced concentration of oxygen. High temperatures and / or metals

  will also accelerate the polymerization.

  According to the present invention, there are provided curable rubber compositions

  under anaerobic conditions that can be applied

  from a form or form such as leaves, ribbons, etc., and who, when

  they are hardened, have rubbery characteristics

flexible and flexible.

  For convenience, the curing of the compositions according to the present invention will be referred to as "cold vulcanization" and is defined as an anaerobic curing of segments.

  Long liquid chatter or non-vulcanized rubber

  derived from a polymer material of high molecular weight

  with appropriate values of density of

  culation to ensure rubbery properties.

  These rubbery properties (elasticity of the rubber

  rubber) are all properties ranging from a highly elastic response to a tenacious flexible material having

  high modules. A definition of elasticity

  In the Textbook of Polymer Science by F.W. Billmeyer (John Wiley and Sons, 4th Edition,

1966), page 189.

  The composition according to the present invention comprises a synthetic rubber composition in combination with one or more anaerobic resins, one or more initiators, an accelerator and an inhibitor. The synthetic rubber composition may also contain fillers such as titanium dioxide, glass, nylon fibers and / or

  polytetrafluoroethylene ("Teflon").

  In one embodiment of the present invention, the anaerobically curable rubber composition is in the form of a tape or tape and may be coated with nylon or other polymer. A strip or ribbon is defined as a manufactured article whose width

is less than the length.

  In general, the synthetic rubber has a molecular weight of from about 50,000 to about 500,000 and is present in a proportion of about 30% to about 80% by weight based on the total weight of the total composition. The anaerobic monomer, which must be soluble in or completely miscible with synthetic rubber, is present in a proportion of from about 70% to about 20%.

  by weight relative to the total weight of the resin.

  The fillers, when present, comprise from about 5 to about 20% by weight of titanium dioxide, glass and / or nylon fibers.

  and from about 0% to about 10% by weight polytetracture

  fluoroethylene. These proportions are taken in each case in relation to the total weight of rubber

synthetic.

  One or more initiators, in a total proportion of between about 0.1 and about 7% by weight relative to the weight of the anaerobic monomer,

  are incorporated in the composition.

  Accelerators, when present, are in a proportion of about 0.1 to about

7% by weight.

  Inhibitors are present

from about 25 to about 1000 ppm.

  The present invention relates to

  which when hardened under anaerobic conditions arrive at rubbery properties. As used in this

  description, the expression "anaerobic monomer" means

  a monomer having at least one, preferably two terminal portions of polymerizable acrylate ester,

  normally at the ends of a chain, which

  risera or harden in the presence of an initiator

  the almost complete absence of oxygen or air.

  One of the particularly preferred groups of anaerobic monomers that can be used in the

  The present invention consists of

  acrylates which have the following general formula:

0 _ 1 R22 0

  Wherein R 1 represents a radical selected from hydrogen, a lower alkyl group having from 1 to about 4 carbon atoms, a hydroxyalkyl group having from 1 to about 4; carbon atoms and

0

- CH2 - 0 - C - C = CH2

  R2 is a radical selected from hydrogen, halogen and lower alkyl having from 1 to about 4 carbon atoms; R3 is a radical chosen from hydrogen, the hydroxyl group and o

- O - C - C = CH2

  te2 m is an integer at least 1, for example from 1 to about 15 or greater, and preferably from 1 to about 8 inclusive; n is an integer at least 1, for example from 1 to about 20

  or bigger; and p is selected from zero and 1.

  Non-limiting examples of polyacrylate esters useful in the invention and corresponding to the above general formula are the

  following: di-, tri- and tetra-dimethacrylate

  methylene glycol, dipropylene dimethacrylate

  glycol, polyethylene glycol dimethacrylate, dimetha-

  di (pentamethylene glycol) crylate, diacrylate

  Tetraethylene glycol, di- (chloroacrylate) tetra-

  ethylene glycol, diglycerol diacrylate, tetra-

  diglycerol methacrylate, tetrachloride dimethacrylate

  methylene, ethylene dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, the reaction product of hydrogenated bisphenol A with

  2,4-tolylene diisocyanate and 2-hydroxy-methacrylate

  and the reaction product of methylene diphenyl-

  isocyanate and 2-hydroxy-methacrylate or 3-hydroxy-

  methacrylate. The previous monomers need not be in a pure state; they may be commercial products in which inhibitors or stabilizers, such as quinones, are included. Monoacrylate esters, in particular esters in which the non-acrylate portion of the ester contains a hydroxyl, mercapto or amino group or other reactive substituent which serves as a site for potential cross-linking with the ester itself and / or with synthetic rubber, can be

used too.

  The choice of anaerobic monomer that can be used in the present invention depends on the particular synthetic rubber selected. The anaerobic monomer must be soluble or completely miscible

  with the synthetic rubber composition.

  The solubility or miscibility of the monomer in the rubber can be easily determined as follows: (1) if the synthetic rubber is a liquid and the anaerobic monomer is a liquid, then

  visual examination will indicate solubility or miscibility

  bility; (2) if the synthetic rubber is

  Then, after mixing the monomer with the rubber, the mixed material is placed on paper. An oily wet spot appears on the paper if the monomer is not soluble in

  rubber or completely miscible with it.

  The term copolymer as used

  in the present description means rubbers

  synthetic copolymers of the copolymer type which are preferably polar and of a molecular weight sufficient for their viscosity to be sufficiently high

  to form stable compositions with the monomers.

  The preferred copolyners have a vinyl group or terminal and / or pendant reactive sites for possible reactions with the anaerobic monomers and are

  preferably, unvulcanized gums.

  Examples of copolymers or rubbers which may be used in the present invention are acrylonitrile / butadiene copolymers having reactive end groups such as carboxy, mercapto or amino; polybutadiene; polyisoprene; butadiene rubber / styrene, polyurethanes

  and acrylonitrile / butadiene / styrene rubber.

  Acrylonitrile / butadiene rubber is available from B.F. Goodrich Co. under the trademark Hycar and the preferred copolymer has an average molecular weight of from about 50,000 to

About 500,000.

  Butadiene-styrene copolymer is called SBR and generally has a ratio of butadiene

styrene about 78:22.

  The acrylonitrile / butadiene / styrene copolymers preferably have an average molecular weight of from about 5,000 to about 100,000 and contain from about 15% to about 35% acrylonitrile.

  and from about 15% to about 55% butadiene.

  The catalyst or initiator for this system

  is composed of a peroxy compound and a co-

  initiator. The preferred peroxy initiators are the

  hydroperoxy initiators and in a particular way

  preferably organic hydroperoxides having the formula R400H, wherein R4 is generally a hydrocarbon radical containing up to about 18 carbon atoms, preferably an alkyl group,

  aryl or aralkyl containing from 1 to 12 carbon atoms

  about bone. Typical examples of such hydroperoxines

  are cumene hydroperoxide, hydroperoxide

  tert-butyl and methyl ethyl ketone hydroperoxide.

  However, other

  peroxides, such as hydrogen peroxide, dihydro-

  peroxides or materials such as certain peroxides

  organic or peresters that hydrolyze or decompose

  pose to form hydroperoxides and dihydro-

  peroxides. Examples of such peroxy initiators are benzoyl peroxide and 2,5-dihydroperoxide.

  2,5-dimethylhexyl. These compounds are known.

  Co-initiators which are useful in the present invention are the known hydrazine derivatives which are capable of causing radical polymerizations at temperatures below about 100 ° C, and especially compounds having the formula

R1 N - N - C - R2

  !! Wherein R 1 may be selected from the following groups: alkyl, preferably lower alkyl containing 1 to 6 carbon atoms, straight chain

  or branched, in particular methyl, ethyl or iso-

  propyl; cycloalkyl containing up to about 8 atomic

  carbon mon; alkenyl containing up to about 10, preferably 2 to 5 carbon atoms; cycloalkenyl containing up to 10, preferably up to about 6 carbon atoms; aryl, including halo-aryl, hydroxy-aryl nitro-aryl and aryl substituted with alkyl or lower alkoxy groups containing from 1 to about 6 carbon atoms. R2 may be hydrogen or any of the radicals specified for R and further may be an amino or substituted amino group,

  or a carbonyl group to which a non-group is attached

  reagent such as a lower alkyl group containing

  from 1 to about 4 carbon atoms.

  Representative compounds responding

  in the formula above are, for example, 1-acetyl-

  2-phenylhydrazine, 1-acetyl-2 (p-tolyl) hydrazine,

  1-benzoyl-2-phenylhydrazine, 1- (1 ', 1', 1'-tri)

  fluoroacetyl) -2-2-phenylhydrazine, 1,5-diphenyl-

  carbohydrazide, 1-formyl-2-phenylhydrazine,

  1-acetyl-2- (p-bromophenyl) hydrazine, 1-acetyl-2- (p-

  nitrophenyl) hydrazine, 1-acetyl-p- (p-methoxyphenyl) hydrazine, 1-acetyl-2- (2'-phenylethyl) hydrazine and

1-acetyl-2-methylhydrazine.

  The efficiency of the accelerators according to the present invention seems to require the presence of a proton on each of the nitrogen atoms, but not more than one proton on each nitrogen atom. If this criterion is satisfied, the precise nature of the R groups does not seem

  not be of critical importance, from the moment evidently

  that the R groups are not chosen in such a way that

  significantly alter the characteristics of conserva-

  adhesion composition or accelerator behavior for the desired purpose. Thus, the selection of particular R groups and their combinations

  is considered to be a question of experimentation

  tion and choice. Those skilled in the art will understand that,

  demo, the optimal choice of R groups may depend on the curable ester monomer or the monomer mixture, as well as the initiator or co-accelerator

possible used.

  The accelerators may be used in amounts of from about 0.001 to about 10 percent by weight or greater relative to the total composition. Below the lower limit

  above, there will be little effect. The upper limit

  is not critical, as we will not usually observe

  There is no significant improvement over

  portions of about 5% by weight. In practice,

  proportions between 0.1 and 2.0o by weight

  will have an optimal overall advantage and this interval

is therefore especially preferred.

  Accelerators are also used

  frequently in compositions according to the present invention.

  vention. Examples are organic amides like

  formamide, succinimide, etc .; tertiary amines

  such as tributylamine, triethylamine, etc., aromatic tertiary amines such as dimethyl p-toluidine, etc .; and organic sulfonamides such as benzoic sulfimide, etc. The accelerators when they are present are in proportions of between about 0.1 and about 70% by weight and

  preferably between 2 and 3% by weight.

  Stabilizers or inhibitors used in the present invention include benzoquinone,

  naphthaquinone, hydroquinone, monomethyl ether

  than hydroquinone, phenols with an

  steric inhibition, etc. The concentration of inhibi-

  It is from about 25 to about 1000 ppm.

  The products according to the present invention may contain any other ingredient which does not significantly modify the anaerobic properties or

  does not affect the formulation of the compositions. Examples

  ples of such additional ingredients are

  such as titanium dioxide, tetrafluoro

  ethylene, glass, nylon fibers, etc., that for convenience is usually added to the copolymer; coloring agents, plasticizers, etc.

  The compositions or products of the present

  The invention may be prepared in a number of ways, such as, for example, in the form of pellicles, ribbons, sheets or a layer on a releasable support. The composition may be extruded, calendered or deposited from a solution, slurry or latex, depending on the intended use

  for the product and the physical properties of the

  mixed position. The solution, slurry or latex can be used "as is" without deposit

  intermediate on another medium, like a painting.

  Products formed from the compounds

  of the present invention have particular utility when applied in the form of a tape to threaded elements such as

  pipe fittings. In this application, they replace

  the tetrafluoroethylene tape currently in use and provide superior sealing performance, and withstand the effects of pressure and solvents. By curing, the product will retain its flexibility characteristic and if it is applied to threaded elements, such as pipe threads, the cured product will play a dual role.

sealing and fixing.

  For convenience in storage and use, the products or compositions of the present invention may be coated with a diaper

  thin of a polymeric material, such as nylon. The coating

  polymer, while being thick enough to allow the ribbon to be rolled up and pocketed

  sticks to itself, however is thin enough to

  put to air to pass through the coating for

to arrive at the ribbon.

  When the product is coated with a polymer, the coating material must be soluble in the alcohol and is usually deposited on the uncured polymer composition from an alcoholic, preferably methanolic, solution. Nylon 6-12 (Du Pont 801 Elvamide) and 12-12 Nylon (Vestamid X1874, X2191 and X2302) were used

for coatings.

  The products according to the present invention described herein, whether in their natural form or in a pre-applied form, are storage stable articles capable of withstanding the conditions

  normal storage and transportation. They do not poly-

  will not deserve (harden) as long as they are

  kept in reasonably thin sheets (as

  1.3 cm or less) and in contact with air or other sources of oxygen. When trapped between non-porous surfaces or otherwise placed in an oxygen-free atmosphere, hardening

  of the composition occurs. The hardened product has

  characteristics of a vulcanized rubber and may consist of the reaction product of the copolymer and the monomer, the complete intermingling of the copolimer in the polymerized monomer or a combination of both.

  The polymerized product, which has the characteristics

  characteristics of a vulcanised rubber, can be distinguished

  to cure untreated reaction products by its extractibility. The unpolymerized reaction products are soluble in organic solvents while

  that the polymerised product is insoluble in soil

  organic substances or can not be extracted by them. The polymerized product is non-extractable at from

  minus 75%, b and preferably 80%.

  The product after curing retains

  flexibility, forms a joint that withstands

  It is 105 to 175 bar and solvent resistant. These

  characteristics are kept in a wide range of

  temperature range of about -54 to about 2040C.

  Although hardening occurs normally

  at room temperature, it is possible to reduce the

  the time required to obtain the hardening

  putting the assembly containing the composition at moderate temperatures, such as from about 38 to about

953 C.

  Sodium salt of ethylenediamine acid

  tetracetic acid, when used in the composition, may be added to the monomer composition or

copolymer-monomer composition.

  The following examples are given to illustrate typical compositions according to the invention, methods of preparation and use of these compositions. They should not be considered as limitations to the invention. Unless otherwise specified, all ratios and percentages in

examples are by weight.

EXAMPLE I

  A curable monomer composition is prepared under anaerobic conditions by mixing the ingredients shown in Table I in the

  approximate proportions indicated.

TABLE 1

Ingredient Weight (grams)

Polyethylene dimethacrylate

  glycol (average molecular weight 330) 100 1-acetyl-2-phenylhydrazine 0.002 Benzoic sulfimide 1.6 Cumene hydroperoxide 3.0 Solution of 1,4-pnaphthaquinone (100 ppm in methanol) 0.2 A mixture consisting of 50 grams of acrylonitrile / butadiene (Hycar 1492) and 20 grams of titanium dioxide mixed in a Waring blender are added 25 grams of the mixture of Table I

  and 1 gram of a solution of ethylenediamine tetra-

  sodium acetate (73.5% methanol, 23% water and

  3.5% sodium ethylenediamine tetracetate).

  The resulting mixture is processed in a rubber roll mill until the lumps disappear and then extruded through a flat die about 0.5 mm thick. The material

  extruded is then passed between cylinders re-

  heated coolers modified (only one cylinder is

  heated) having a spacing of about 0.076 microns.

  The resulting material, which is in the form of a ribbon about 0.05 to 6.35 mm thick, is applied to a strip of release paper

and wound on reels.

EXEIPLE 2:

  Prepared as in Example 1 a

  anaerobic copolymer-monomer mixture.

  The resulting mixture was extruded through a flat die about 0.5 mm thick. The

  extruded material is then passed between cylinders

  heated chillers modified as in

the exemaple 1.

  After leaving the cooling cylinders

  dissectors (calender rolls), the material was passed through a solution of nylon 6-12 (6-7% nylon 6-12, in methanol) and then through a column of air heated to about 520C. Methanol

  is evaporated in the treatment with heated air, revived

  both the rubber tape and the nylon layer of

* about 13 to 25 microns thick and the coated tape is then wound on a paper reel without any

  layer of paper separating the ribbon layers.

  To use the tape, place it on the threads and extend to break the coating

of nylon.

EXAMPLE 3

  To a mixture of 50 grams of acrylonitrile / butadiene (Hycar 1492), 19.5 grams

  of titanium dioxide and 0.5 gram of tetrafluoro-

  ethylene, mixed in a Waring blender, grams of the mixture of Table 1 and 1.5 grams of a solution of sodium ethylenediaminetetraacetate (73.5% methanol, 230% o water and 3.5% d 'ethylene-

sodium diaminetetraacetate).

  The resulting mixture is processed in a rubber roll mill until the lumps disappear and then extruded through a flat die about 0.5 mm thick. The extruded material is then passed between cylinders

  heated chillers modified as in Example 1.

  Upon leaving the calender rolls, the material was passed through a 6-7% nylon 6-12 solution (in methanol) and then through a column of air heated to about 520 ° C. The methanol is evaporated in the treatment with heated air,

  covering the rubber tape with a layer of nylon.

  This ribbon, in its uncured state, has a shelf life of more than one year. In its cured state, the tape has an elongation of 470 / o, an apparent tensile strength of 6.9-MPa and is usable in the temperature range of about

-54 to about 20400.

  The tape was applied to form a malleable seal for 9.5 mm iron tees, subjected to a torque of 2.76 m 2 kg, and subjected to stress tests with the following results: the joints, immediately after

  assembly or after curing for 24 or 48 hours

  do not leak when subjected to a hydraulic pressure exceeding 140 bar; b) no leakage occurs when the assembled tees (with curing for 24 hours) are subjected to temperatures between about 9,300 and about 2040C for a period of 500 hours and subjected to pressures of about 105 bar; c) no leakage occurs at pressures up to 211 bar (after

  cured were cured for 24 hours.

  res) when immersed in the following solvents at the indicated temperatures for eight weeks; transmission fluids (149 C); engine oil (149 C); glycol / water (132 C); gasoline (82 C); and air (87 C); d) several tees (after curing for 24 hours) that have been subjected to 95% humidity at 38 C for 1000 hours do not show any leaks

  after pressurizing to 140 bar.

EXAMPLE 4

  The mixing and the operation are repeated

  Example I using hydroperoxide from

  t-butyl instead of cumene hydroperoxide.

EXEIPLE 5:

  To a mixture of 75 g of acrylonitrile / butadiene (Hycar 1494) and 20 g of titanium dioxide, mixed in a Waring blender, 25 g of

  mixture of Table 1 and I g of an ethylene

  sodium diamine tetracetate (73.5% methanol, 23% water and 3.5% sodium ethylenediamine tetracetate). The resulting mixture is processed in a rubber roll mill and passed between calender rolls to give a material under the

  form of a film 0.5 mm thick.

EXAMPLE 6

  At 186 grams of a 20% solution of Hycar

  1492 in methyl ethyl ketone, successively

  by providing a complete dissolution of a compound or a mixture with the addition of the following compound or mixture, 40 grams of triethylene glycol dimethacrylate, 22.5 grams of an 80% solution in toluene of a dimethacrylate formed from the

  reaction product of toluene diisocyanate, bis-

  hydrogenated phenol A and 2-hydroxyethyl methacrylate;

  and 2.4 grams of 2,5-dimethyl-2,5-dihydroperoxide

  hexyl. The temperature during all the addition is

maintained below 40 C.

  The resulting solution was applied to a release paper and the solvent was evaporated leaving a dried and uncured film 0.05 to 0.25 mm thick. Drying of the film (evaporation

  solvent) occurs at a temperature no higher than

only 52 C.

EXAMPLE 7

  Non-hardened materials are obtained which are

  tables, in the form of ribbon and foil, using the following anaerobic copolymers and monomers in the procedure of Examples 1,

2 and / or 5.

  Copolymer a) butadiene / methacrylate having a pendant unsaturation b) acrylonitrile / butadiene c) butadiene / styrene d) acrylonitrile / butadiene

having groups terminating

  carboxy e) butadiene / styrene f) butadiene / acrylate / methacrylate g) acrylonitrile / butadiene Treatment Polyethylene glycol dimethacrylate monomer lauryl methacrylate tetramethylene glycol dimethacrylate

3- methacrylate

hydroxypropyl

% styrene / 20% dimetha-

pentate crylate

  ethylene glycol pentaethylene glycol dimethacrylate

methacrylate of 2-

hydroxyethyl from the final product by

  extrusion, calendering or removal from a

  depends on the ease of treatment and the

  physical properties of the product. Most products are a gum or foldable solid material that can

  extruded without the use of excessive force.

  If the product is of a nature that is not easily

  Extrudably, it can be processed between calender rolls or by pouring out a solution.

Claims (22)

  1. A cold vulcanizable rubber composition, characterized in that it comprises: a) from about 30% to about 80% by weight   of a copolymer selected from an acrylonitrile copolymer   trile / butadiene having an average molecular weight of from about 50,000 to about 500,000 and   having terminal or pendant vinyl groups, a co-   acrylonitrile / butadiene polymer having tertiary groups   carboxy, mercapto or amino reactive reagents, poly-   butadiene, polyisoprene, acrylonitrile / butadiene / styrene copolymer and butadiene / styrene copolymer; b) from about 70% to about 20% by weight   of an anaerobic monomer that is soluble in the copo-   lymere or miscible with it; c) from about 0.1% to about 7% by weight,   relative to the weight of the anaerobic monomer, a system   catalytic system; d) an accelerator; and e) a stabilizer, which composition can be polymerized, in   anaerobic conditions, in a matter of molecular mass   high level of properties similar to those of a vulcanized rubber, having at least 65% non-extractable solids.   2. A composition according to claim 1, characterized in that the anaerobic monomer has the general formula 0 1 R2   H2C = C 0 C [- (CH2) m- - c 0 - = CH2 P n wherein R represents a radical chosen from hydrogen, a lower alkyl group having   1 to about 4 carbon atoms, a hydroxy group   alkyl having from 1 to about 4 carbon atoms, and - CH2 - 0 - C - CH2 2 R2   R is a radical selected from hydrogen, a halogen and a lower alkyl group having from 1 to about 4 carbon atoms; R3 is a radical selected from hydrogen, hydroxyl radical, and o - O - C - C - CH2 à2   m is an integer at least 1; n is a name-   an integer of at least 1; and p is zero or 1.   3. A composition according to the   2, characterized in that the copolymer is an acrylonitrile / butadiene copolymer having groups   terminal or pendant vinyl and having a   mean angle between about 50,000 and About 500,000.   4. A composition according to claim 3, characterized in that it contains a filler in a proportion of about 5% to about 2% by weight by weight. relative to the total weight.   5. A composition according to claim   3, characterized in that the catalytic system comprises   a peroxy initiator selected from oxygenated water, the hydroperoxides having the general formula R400H wherein R4 is a hydrocarbon radical having from 1 to 12 carbon atoms selected from alkyl, aryl and aralkyl radicals, peroxides, peresters and dihydroperoxides, and as co-initiator a   hydrazine derivative capable of causing polymerisation   free radical at temperatures below about 100 ° C. 6. A composition according to claim 5, characterized in that the peroxide initiator is cumene hydroperoxide and the co-initiator is 1-acetyl-2-phenylhydrazine.   7. A composition according to the   6, characterized in that the accelerator is   chosen from organic amides, tertiary alkylamines   tary amines, aromatic tertiary amines and an organic sulphimide.   8. A composition according to the   7, characterized in that the accelerator is a organic sulfimide.   9. A composition according to the   8, characterized in that the organic sulfimide is the benzoic sulfonamide.   10. A composition according to the   9, characterized in that the stabilizer is selected from benzoquinone, naphthoquinone,   hydroquinone, the monomethyl ether of hydroquin   none and phenols with a steric hindrance than.   11. A composition according to the   cation 10, characterized in that the stabilizer is naphthoquinone.   12. A composition according to claim 11, characterized in that the anaerobic monomer is   polyethylene glycol dimethacrylate.   13. A composition according to the   12, characterized in that the polyethylene glycol dimethacrylate has an average molecular weight about 330.   14. A composition according to the   13, characterized in that the copolymer is   about 60 to about 75% in weight.   15. A composition according to the   14, characterized in that the anaerobic monomer is present in a proportion of about 20 to about 50% by weight.   16. A composition according to the   15, characterized in that the load is selected   among the titanium dioxide in a proportion of about   to about 20% by weight and polytetrafluoroethylene   ethylene in a proportion of about 0 to about 10% by weight, the total weight of charges not exceeding about 20% by weight, relative to the total weight of the composition.   17. A composition according to the   16, characterized in that the filler is a mixture of titanium dioxide in a proportion of about 18 to about 19.5% by weight and tetrafluoroethylene in a proportion of about 0.5 to about 2% by weight. weight.   18. A composition according to the   16, characterized in that the filler is titanium dioxide in a proportion of about 18 to about 20% by weight.   19. An article in the form of a tape having a thickness of about 0.05 to 6.35 mm, usable as a sealant and formed from a composition of any one of claims I to 18.   20. An article according to claim 19, characterized in that it is coated with a polymer coating having a thickness of between about 13 and 25 microns, this coating allowing the air to reach the rubber composition.   21. An article according to claim 20, characterized in that the polymer coating is nylon 6-12.   22. An article in the form of a sheet having a thickness of between about 0.05 and 0.38 mm, usable in the preparation of a joint material or as a support material and formed from a composition according to any one claims I to 18.